Process for producing pour inhibitors for wax-containing oils



Patented July 1Z0, 1937 rrtocEss Fon PRODUCING POUR INHIBL 1 x,;"-TRS F0R WAX-CONTAININGOILS a g a H Garland H. B. Davis, Baton Rouge juLa-i ay]: I i i Charles C. Swoope', Bayonne, N. J., as'signorsfi I to Standard Oil Development Company a a 14 Claims. The present invention relates, to, theart of producing oils of low coldfltest fromoils containing waxy hydrocarbons, and more specifically,

' toan improvedgmethod for preparing a pour inhibiting substance which may be added to the wax-containing oils.. The invention will be fully understood from the following description:

In a prior patent U. s. 1,815,022 issued July- 14,-

193 1, a process for producing low. cold test oils from. wax-containing hydrocarbons is disclosed;

In this patent theparticularmethod disclosed.

inhibiting purposes, the condensation is pref-q erably carried out between a chlorinated derivative of paraflin wax and a hydrocarbon such as.

25 naphthalene at low temperatures, saywfr'om room temperature .to about 160 F. But itawas. stated that at the end of the reaction, or-' in .order to force the reaction to its conclusion thetemperature is gradually raised to about 200,F: and held 30 at that point for ashortwhile. The purpose of this step was stated to beI'in order to bring the reaction to its conclusion and, furthermore, it

served to put the aluminous sludge-in such a; condition that it might be readily'settled from the oil. It has now been discovered thatit is preferable to keep the temperature at all times below about 125 F., or even lower, for example, at 100, F., and todiscontinuethe reaction before it.has reached its final stage. In this manner 40 especially powe'rfulinhibitors can be produced.

Furtherreaction does not -entirely destroy theinhibiting properties of the product,,but the dee sired property appears to reach the optimum at a certain stage of the reaction'and to decrease if 45 the further chemical change is allowed topro-- ceed. But this-proposed method of stopping" the reaction before reaching-its final stage hasseveral objections thechief of which is that under such conditions, and especially when relatively 50 small proportions of aluminum chloride are used,

there is great difliculty in bringing-about a sep-:

aration of the sludge and the recovery'of the oily, product, I t

It has been discovered, however, that the sludge 5 produced in the intermediate stages of the reabout; 650 F., and-the resi I No Djrawing Application :Noyember 19, 91 I k I -Sei'ial No.576,208 V action may-bezreadily broken outand removed Y by theadditionutof ai'suitablefhydrolytic agent suchaas-water or alkali= either of which haslthe powerto. decompose thealuminum chloride cata-fi; J lyst,-or othermaterialsof; thesame class 'suchas L5 zinc chloride, iron chloridepjand borons' flu'oride.

' The products of the'hydrolysisias' well as' the excess-of the hydrolyzing agent; maybe readily removed, from theifoil either :by-msettling, or by centrifugalfmeans; =.or -in'any other satisfactory 10 manner; There sometimesfdifilcultyg0ndac-". count of emulsification, and-insucli cases-the addition of-a small amountv of alcohol 2,3, -5or 10% 3 of=ethyl, ,or isopropyl, or other water soluble-alco hols,= or other: equivalent materials, are useful i addition agents to break or prevent the formation of emulsions." While caustic soda, or11carbonate is usuallypreferred as thehydrolytic agent, other alkalis maybe used such as ammonia, potash; or a slurry of lime. After'the aqueous, layenhas been removed the oil maybe washed with water or'm a'y be .finished;inyany other means,;for ;example,'1t -may; be washedwith; other. suitablegpurifying v agents and/ortreatedwithclayeither. in a finely g 7 divided form, or the oil maybe allowedzto; per- 5 colate through a bedof clay of large particle'size. This latter treatment produces a lighter colored- :stockforblending purposes; Lowerboiling' por- 'tions of the condensation. product and the waxy I products may be removed by; distillation. in which the temperatureis preferably 'held ,atjorsbelow ue containingth'e'i" active'pourinhibitor is recovered.

j It will be understood that'the power: or potency r ofxth'e condensationproduct for pour inhibiting purposes isdependentson many factorspfor exa ample, it is found that the chlorparafiin o'r' other,

halogenide varies with difierent grades of wax I and with, different temperatures ofchlorinatiohQ Wax free-bf oil is preferred, or atleast, with a relatively small proportion say-11.5 to 2% of oil and the temperature from 130 to 300 -F. is,preferred for chlorination, which isdallowed totproceed preferably:- to' about 12%. About l5 parts by weight. of naphthalene or other aromatic hydro-' carbons to about 101) *of the chlorinated paraffln' is perhaps the most desirable proportion, although it maybe, varied without greatly changing the ,pour inhibitingproperties, and may be quite different with other aromatics. Obviously, it is desirable; to use as little of the aluminum chloride, or=other catalyst, as possibleand 7 pounds per 100 poundsof chlorinated paraflin has'beenjfound s to'be'quite'satisfactorya Five'pounds appears to I.

be equally good'and even smaller amounts say 3 or 3 /2 pounds may be used, but in such case there is even greater difiicultyin separating the sludge from the oil and greater need for the improved method of separation. The catalyst may be added all at once or slowly or at intervals of time such as every or hour or every hour until the total is used. p a

Whensmall amounts of aluminum chloride are used greater care should be taken to obtain violent and thorough agitation. Temperature.

should be maintained as low as possible with due regard to a commercial rate of reaction." With a high degree of agitation lower temperatures are permissible, and for large scale commercialequip- F ment 125 F. or 110, or even? 109 or 70 F. have been found satisfactory. n V

The most suitable time of reaction is, of course, dependent on the temperature, the particular catalyst and the amount of it used. At lower. temperatures shorter times are required. At 80 R,

for example, in a large scale unit; with the best possible agitation andwitha'bout 5 pounds of aluminum, chloride per. 100 pounds of "chlorparaffin, a time of 2 to '10 hours was satisfactory; but'in thiscase it isnoted that the reaction has not reached its'final stage, and by this is meant that further internalchanges'will still take place ifadditional time is provided. A time of 5 or 6 hours is perhaps. most-satisfactory under the above conditions, and at this time the amount of chlorparafiin is reduced below 5-% of the original amount. The aluminous sludgeis usually found to be extremely 'diificult to settle. In fact, it may be said: that the best pour inhibiting prodnot is produced during the time interval". when the chlorparafiin is/reducedlto below 3, or 2 or -may be considered: a

IOU-parts ofchlorinated'parafiin. wax is propreferably 1% of the original quantity and the time when'settling becomes rapid: The best time to discontinue is when the chlorparafiin is below 1% oreven completely exhausted and when settling is mostdifficult, although, of course, it'is difficult to stop at this precise point-at which -all chlorparaflin has just reacted. During this time or at this particular point, however, separation of the material by means of a 'liydrolytic agent'is relatively easy. As an illustrativeexample of the improved operation the following experiment pared by passing chlorine through a melted wax which contains less-than2% of oil.-- The chlorina-x tiontakesplace..in;about 20 hours, and tothis' product, which containsabout 12%; chlorine, 15 parts of naphthalene are added. The whole is now brought in solution by the addition of 175 partsof. a good grade-of kerosene; 3' parts of anhydrous aluminum chloride are slowly added while the mixture is held at a temperature of about 85-1F. and thoroughly agitated. A jack-' eted vessel is satisfactory for this purpose. After 2 hours an aliquot part is removed and the reaction is stopped by hydrolyzing with aqueous caustic soda to whichx3% "of isopropyl alcohol has been added. The sample is finished by re-' hibiting powers are preserved. 2. Anvimproved process for producing valuable oil to -5 F. when used in 1% proportion. The amount of chlorparaflin inthe second sample is practically negligible being below. 1% and the sludge cannot settle of itself. Continuing the reaction further produced less reactive pour inwith lessdifiiculty. L. .v v

. The above description is based on the use of chlorinated paraffin wax but it should be unhibitors although the sludge a'ppearedto settle- .derstoodthat other halogenated derivatives or olefines derived from parafiin wax, for example, by -formationof olefines byjsplitting out hydrochlori'c acid from chlorparafiin by known meth-' ods, may be used in place of andare the equivalent" ofthe chlorinated wax. Similarly, the arcmatics maybeeliminated, and condensation or polymerization of. chlorparaflin or other halogenides, or'other olefines derived from paraffin, or mixtures of these substances, may be used to produce excellent pour-inhibitors by this method.

In the following claims when the terms condens'ation' product derived fromparaffin wax or a from paraffin'wax and' naphthalene areused, it

is'intended to include thecondensatio'n productof the active wax derivatives disclosed above whether produced by' chlorination or'by first ob tainingthe olefineand either produced in the presence o'r in thefiabsence of aromatic hydrocarbons. I

The invention is not tobe limited by any theory of the mechanism off pou'r reduction, nor by the chemical reactions involved in the preparation of the pour inhibitors=or 'WhichJmay occur in the pourinhibiting process,'-but 'onlyto the following claims in whichit is desired to'claim allnov elty. inherent in the invention. j I

We'clairn: I v a 1..An improved process 'for producing con-- densation products valuable as pour inhibitors comprising the steps'of bringing about acondensation of a 'materialselected-from the group consisting :of a halogenated waxy hydrocarbon or-olefins of the type derived fromsaid haloperature under the influence of a catalyst of the aluminum chloride type, stopping the reaction be-:

fore its normal conclusion whereby-valuable inpour inhibiting substances comprising the steps of condensing a material selected from the group of'substances consisting of chlorinated derivagenated hydrocarbons at a low condensation teme;

tives of paraffin wax or olefins derived therefrom through the'agency of a catalyst of the aluminum chloride type, stopping the" reaction before its normal conclusion at .a point when the aluminous sludge settles with difiiculty, and recovering the oily product. A

3.. An improved process for producing valuable pour. inhibiting-substances comprising the steps of condensing active derivatives of para'fiin wax selected from the group consisting of chlorinated wax 'orolefins' derived therefromthrough the agency of a catalyst of the aluminum chloride type, stopping the reaction'by addition of a hydrolyzing'agent'at the-point before the final stage ofthe reaction so as to provide a. reaction time of 2 to .10hoi1rs'and where pour inhibiting powers are at a substantial maximum, separating the hydrolytic products of the catalyst and recovering the oily product." 1 V 4. Animprovedtprocess fo'r'producing valuable pour inhibiting substances comprising the'steps of condensing active derivatives of parafiinwax selected from the group consisting of chlorinated wax or olefins derived therefrom at a. temperature below 125 F. through the agency of aluminum phloride, stopping the reaction after a time of about 2 to 10 hours before the final stage, when less than 2% of the active derivative of the wax remains, and when the aluminous sludge settles only with difiiculty, by addition of an aqueous agent for hydrolyzing the aluminum chloride, separating the products of hydrolysis and recovering the oily product.

5. Process according to claim 4 in which an aqueous alkali is used as ahydrolyzing agent.

6. Process according to claim 4 in which the hydrolyzing agent comprises aqueous alkali to which a small amount of a soluble alcohol has been added.

7. An improved process for producing valuable pour inhibiting substances comprising the steps of producing a condensation product of chlorinated parafiin wax through the agency of a catalyst of the aluminum chloride type, stopping the reaction by addition of a hydrolyzing agent at a point before the final stage of reaction and where pour inhibiting powers are at a substantial maximum, separating the hydrolytic products of the catalyst. and recovering the oily product.

8. An improved process for producing valuable pour inhibiting substances comprising the steps of producing a condensation product of chlorinated parafiin wax at a temperature below 100 F. through the agency of aluminum chloride, stopping the reaction before the final stage after a reaction time of about 2 to 10 hours, and where the aluminous sludge settles only with difficulty, by addition of an aqueous agent for hydrolyzing aluminum. chloride, separating the products of hydrolysis and recovering the oil product.

9. An improved process for producing valuable pour inhibiting substances comprising the steps of forming a low temperature condensation product of chlorinated parafiin wax on an aromatic hydrocarbon through the agency of a. catalyst of the aluminum chloride type, stopping the reaction by addition of a hydrolyzing agent after a reaction time of 2 to 10 hours and before the final stage of reaction where pour inhibiting powers are at a substantial, maximum, separating the hydrolytic products of the catalyst and recovering the oily product.

10. An improved process for producing a val uable pour inhibiting substance comprising the steps of condensing chlorinated paraifin wax on naphthalene at a temperature below 100 F.

through the agency of aluminum chloride, stopping the reaction after a reaction time of 2 to 6 hours where less than.1% of the chlorparaiilin remains and where the aluminous sludge settles only with difiiculty' and separating the oilyproduct.

11. An improved process for producing vim-- able pour inhibiting substances comprising the stepsof producing a condensation product of an olefine of the type derived from halogenated paraflinwax through the agency of a catalyst of the aluminum chloride type, stopping the reaction by addition of ahydrolyzingagent at a point before the final stage of reaction where pour inhibiting powers are at a substantial maximum, separating the hydrolytic productslof the catalyst and recovering the oily product.

12. An improved process for producing V3.111-- able pour inhibiting substances comprising the steps of producing acondensation product of an olefine of the type derived from chlorinated paraflin Wax at a temperature below 100F. through the agency of aluminum chloride, stopping thereaction so as to provide a reactiontime of 2 to 10 hours, and where thealuminous sludge I settles only with difficulty, by addition of an aqueous agent for hydrolyzing aluminum chloride, separating the products of hydrolysis and recovering the oily product.

13. -An improved process for producing valu-- able pour inhibiting substances comprising the product of an olefine of the type derived from carbon through the agency of'a catalyst'of the steps of forming-a low temperature condensation aluminum chloride type, stopping the reaction 7 1 by addition of a hydrolyzing agent so as to provide a reaction time of 2 to 10 hours before the final stage of reaction where pour inhibiting powers are at a substantialmaximum, separat ing the hydrolytic products of the catalyst and recovering the oily product. I

14. An improved processfOr producing a valuable pour inhibiting substancecomprising the steps of condensing an olefine of the type derived from chlorinated paraffin, wax on naphthalene at a temperature below 100; F. through the agency of aluminum chloride, stopping the rea reaction time of about 2"to- 6 hours and where the aluminuous sludge settles only with difliculty and separating the oily productyy; v GARLAND v H. 'B. AVIS.- H

CHARLES .C.. .SWO'OPE.

action before the final stage so as to provide 7 

